Photochemistry of the pi-extended 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene system: generation and characterisation of the radical cation, dication, and derived products.
Photochemistry of the pi-extended 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene system: generation and characterisation of the radical cation, dication, and derived products.
复制标题
π-扩展的 9,10-双(1,3-二硫醇-2-亚基)-9,10-二氢蒽系统的光化学：自由基阳离子、双阳离子和衍生产物的生成和表征。
作者：
Allison E. Jones;C. Christensen;Dmitrii F. Perepichka;A. Batsanov;A. Beeby;P. Low;M. Bryce;Anthony W. Parker
双[4.5-二（甲基磺胺基）1,3-二硫醇-2-酰基]-9,10(-二氢蒽(1)在氯仿中的闪光光解导致瞬态自由基阳离子的形成1。+具有诊断性的宽吸收带，在lamdamax约650 nm。这个波段在大约80微米的时间内衰减到原来强度的一半。物种1。+也已被表征共振拉曼光谱。在脱气溶液中而在曝气溶液中，光降解产物是10-[4,5-二（甲基磺胺基）1,3-二硫醇-2-基]蒽-9(10 H) 1(2)。通过电化学光谱研究[lambdamax (CH2Cl2) = 377,392,419,479 nm]和电结晶得到的1(2-)(ClO4)2盐的x射线晶体结构表征了1（2+）。图中平面蒽环与1,3-二硫环形成77.2度的二面角；这种构象与先前报道的中性1的鞍形结构有显著不同。
Flash photolysis of bis[4.5-di(methylsulfanyl) 1,3-dithiol-2-ylidene]-9,10(-dihydroanthracene (1) in chloroform leads to formation of the transient radical cation species 1.+ which has a diagnostic broad absorption band at lambdamax approximately 650 nm. This band decays to half its original intensity over a period of about 80 micros. Species 1.+ has also been characterised by resonance Raman spectroscopy. In degassed solution 1.+ disproportionates to give the dication 1(2+), whereas in aerated solutions the photodegradation product is the 10-[4,5-di(methylsulfanyl) 1,3-dithiol-2-ylidene]anthracene-9(10 H)one (2). The dication 1(2+) has been characterised by a spectroelectrochemical study [lambdamax (CH2Cl2) = 377, 392, 419, 479 nm] and by an X-ray crystal structure of the salt 1(2-) (ClO4)2, which was obtained by electrocrystallisation. The planar anthracene and 1,3-dithiolium rings in the dication form a dihedral angle of 77.2 degrees; this conformation is strikingly different from the saddle-shaped structure of neutral 1 reported previously.